KR20110103285A - Resin composition for block including bottom ash and the block - Google Patents

Abstract

The present invention relates to a resin composition for a block including low ash and a block thereof, and more specifically, by mixing and curing hardly the bottom ash (lowest ash), which is the least used among industrial by-products generated from thermal power plants, in a polymer resin, A technique for manufacturing recycled blocks for use in civil engineering.

Description

Resin composition for blocks containing low ash and the block {Resin Composition for Block Including Bottom Ash and the Block}

The present invention relates to a resin composition for a block including low ash and a block thereof, and more specifically, by mixing and curing hardly the bottom ash (lowest ash), which is the least used among industrial by-products generated from thermal power plants, in a polymer resin, A technique for manufacturing recycled blocks for use in civil engineering.

Due to the rapid development of industry and economy, the demand for energy is increasing rapidly. As a result, coal ash, a by-product of coal-fired power plants, continues to increase. Specifically, domestically produced coal ash has reached 7.6 million tons in 2008, which is increasing continuously.

In general, ash refers to minerals (SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaO, etc.) generated after incineration or combustion of organic materials in thermal power plants, and in coal-fired power plants, incinerators, cogeneration plants, etc. Occurs. However, since the combustion is not completely burned, it contains a large number of coal briquettes, and thus there is a limit in engineering applications.

 Coal ash generated from the power plant is classified into fly ash collected through the dust collector and bottom ash collected below the combustion chamber. In the case of the low ash, the ratio is about 10 to 20%.

Typical characteristics of low ash include particle size distribution of 0.0001 to 25 mm, effective particle size distribution (D ₁₀ ) of 0.008 to 0.03 mm, uniformity coefficient (C _u ) of 1.5 to 25.0, and various particle size distribution. It is 2.0 to 2.7 lighter than general concrete or natural aggregate, the dried unit weight is 720 to 1,600 kg / m ³ , the absorption rate is in the range of 3 to 30%, the particle surface has a porous surface as shown in FIG. And particles that remain unburned by incomplete combustion. The low ash color is different depending on the production environment and components such as gray, yellow, black and gray white. Low ash has various physical and chemical characteristics by discharge area or by discharge power plant, and there is a limit to being used in engineering. Therefore, it is generally used in small amounts together with fly ash as waste landfill in a waste treatment plant, or as subgrade soils around a power plant or elsewhere. Recently, artificial lightweight aggregates or natural aggregates are used due to the issue of low ash processing site and resource recycling. Or research is underway to replace sand.

On the other hand, fly ash has been steadily studied in research institutes and academia, and is currently used as a material for concrete additives, admixtures, landfills, soil improvement materials, lightweight aggregates or lightweight concrete, especially when used as additives in concrete. It is used for reducing agent and high strength concrete compounding, and its recycling rate is about 90%.

Fly ash among the coal ashes generated in domestic power plants is very high in recycling, and most of them can be recycled by themselves.However, low ash is mostly buried in the ash processing plant due to the physical characteristics as mentioned above. It is also unreasonable in terms of aspect. Therefore, in order to prevent the enormous loss of resources and increase the recycling rate of environmentally unreasonable resources, it is necessary to improve the efficiency along with the low-level recycling treatment method, and to solve some of the following problems.

First, treating low ash with a variety of physical properties as a homogeneous property, specifically homogenizing the particle size distribution to ensure quality stability and separate the coal briquette powder, the economical efficiency of the grinding and separation process It has the disadvantage of falling considerably and requiring excessive facility investment.

Second, due to the physical properties such as porosity of the low ash particles themselves and the presence of incomplete combustion particles, even when the low ash particles are connected through chemical bonding such as an alkali reaction such as cement paste, the strength of the composition is difficult to express more than a certain level and quality control There is a difficulty.

Third, the conventional low ash recycling technology is mainly concentrated on the production of lightweight aggregates or lightweight panels, but the field of using lightweight aggregates in the construction field is extremely limited, which may cause difficulties in disposal after mass production.

Fourth, the content of the binder that serves as an adhesive to increase the strength expression using low ash is increased, and thus the ratio of low ash that can be recycled is lowered, resulting in a lower recycling rate.

The present invention has been made to solve the above problems, and an object thereof is to provide a block composition in which low ash is mixed with a resin mixture and an initiator.

Moreover, another object of this invention is to provide the block which hardened the said block composition.

The block composition of the present invention is devised to solve the above problems,

Polymethyl methacrylate: methyl methacrylate = 1: 100 parts by weight of the resin mixture in a ratio of 1 to 10 parts by weight;

100 to 2000 parts by weight of bottom ash filler; And

1 to 15 parts by weight of initiator

Characterized in that it comprises a.

In addition, the resin mixture is

Polymethyl methacrylate: methyl methacrylate = 1: 10 to 99.9% by weight methacrylate mixture in a ratio of 1 to 10, and

Urethane-acrylate resin 0.1-90 wt%

It may be a polymerized mixture of.

In addition, the low ash filler is

Low ash 10 to 99.9% by weight, and

0.1 to 90% by weight of filler material selected from the group consisting of cement, fly ash, sand, gravel, stone powder, silica sand, calcium carbonate, talc, steel slag and mixtures thereof

It may be a mixture of.

In addition, the initiator may be potassium persulfate, ammonium persulfate, sodium hydrosulfite, sodium persulfate, sodium bisulfite, sodium bisulfate, Rongalite C, rongalite Z, benzoyl peroxide, t-butyl hydroxy It is preferably selected from the group consisting of loperoxide, N, N'-azobisisobutyronitrile and mixtures thereof.

In addition, the isocyanate which is a monomer of the urethane prepolymer of the urethane-acrylate resin is polymethylene diisocyanate, tolylene diisocyanate, naphthalene-1,5-diisocyanate, xylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, It is preferably selected from the group consisting of triphenylmethane diisocyanate, 2,4-tolylene diisocyanate dimer, hexamethylene diisocyanate, isophorone diisocyanate and mixtures thereof.

Further, the polyol which is a monomer of the urethane prepolymer of the urethane-acrylate resin may be ethylene glycol, propylene glycol, tetramethylene glycol, poly (tetramethylene ether) glycol, poly (1,4-butanediol adipate) glycol, polycaprolactone diol It is preferably selected from the group consisting of glycols, polycarbonate diols and mixtures thereof.

In addition, the acrylic monomer of the urethane-acrylate resin is preferably selected from the group consisting of ethyl acrylate, acrylic acid, n-butyl acrylate, methyl methacrylate, 2-hydroxy ethyl methacrylate and mixtures thereof.

In addition, the urethane-acrylate resin may be introduced with a hydrophilic functional group by dimethylol propionic acid (dimethylol propionic acid) or N -methyl-2-pyrrolidone ( N -methyl-2-pyrrolidone).

In addition, the urethane-acrylate resin may be neutralized by triethylamine.

On the other hand, the block of the present invention is characterized in that the block composition is cured.

When polymethyl methacrylate alone, more preferably, a polymer resin mixed with polymethyl methacrylate and a urethane acrylate resine is mixed with low ash to form a mixture, the polymer resin is used as a low fine powder. It can play a role to compensate for the weakening of the bond. Specifically, the carbon-bonded polymer material penetrates between the low ash particles and connects the low ash particles to improve the strength of the composition, and distributes the external load to serve to make it possible to recycle low ash which is less useful. Can be.

This recycling technology can be used for the commonly used sidewalk blocks (interlocking block (ILP), permeable block), and can express a strength of 5 MPa or more, which is the reference strength (KS F 4419) required for the sidewalk block for sidewalks. have. In this case, resource recycling can be developed through resource recycling, and polymethyl methacrylate resin, which has characteristics of nontoxicity and chemical resistance, is harmless to the human body by coating fillers such as low ash inside. In addition, it can fundamentally block the generation of hexavalent chromium, which is a problem of the existing concrete mortar.

When manufacturing the sidewalk block using polymer resin, it is possible to increase the size of aggregate that can be used with better adhesive strength than general concrete, and as the size of aggregate increases, the space between aggregate particles is generated, and the sidewalk block itself due to porosity Since the permeability of the can be secured, it can be applied to the permeable block as a result.

In addition, even in the case of the shore block used frequently in the river site, it is possible to manufacture the shore block that can be recycled by high-functional resources by adjusting the density of the filler according to the size and increasing the mixing ratio of the polymer resin.

1 is a photograph showing a typical low particle surface.
FIG. 2 is a diagram showing a polymethylmethacrylate polymerization mechanism produced by mixing methylmethacrylate and benzoyl peroxide.
3 is a photograph showing the bottom ash used in the test.
Figure 4 is a photograph showing a specimen for the production of sidewalk blocks.
Figure 5 is a photograph showing the walkway block bending strength test method and the development process.
Figure 6 is a photograph showing the specimen for the preparation of the relief eye block.
Figure 7 is a photograph showing the procedure submerged in the water for the bending block strength test.

Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, many specific details such as specific components are described in the following description, which is provided to help a more general understanding of the present invention. It is self-evident to those who have knowledge of the world. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The present invention is to improve the strength of the low ash through the chemical fusion with the polymer resin in order to compensate for the problem of low recyclability and the limited demand of the conventional recycling technology due to the general physical and chemical properties of the low By applying to the sidewalk block, raft block and masonry block which are used in the sidewalk and bicycle pavement field which are used in the construction / civil engineering field, it is possible to reduce the unnecessary waste of resources and maximize the recycling of resources. It aims to secure.

In order to solve the above problems, the block composition of the present invention is a methyl methacrylate (MMA) and benzoyl peroxide (benzoyl) having a regular bonding structure that is widely used in industrial LCD panel covers, adhesives, soundproof walls, artificial marble, and waterproof construction. polymethyl methacrylate (PMMA) mixed with peroxide alone or an initiator capable of mixing and curing such polymethyl methacrylate with urethane acrylate resine, which is widely used for industrial and construction roads. It is characterized by including the bottom ash which is waste.

The block composition thus constructed may have a load strength suitable for the target object by internal load absorption and rigidity with respect to external loads generally generated.

Cement, which is usually used as civil engineering and building mortar, not only emits toxic substances (cement poison, Cr ⁶⁺ , various heavy metals, etc.) generated from the cement itself after a certain time, but also dissolves and expands with time after curing. Weathering proceeds due to delamination, erosion by wear, and the like. This results in a change in the mechanical properties of concrete when it is continuously exposed to certain chemicals, resulting in partial or total strength degradation or degradation, which is commonly referred to as neutralization. If the neutralized concrete is saturated with water and frozen, there is a high risk of cracking due to volume expansion and weathering. This is because cement-based concrete structures are generated through alkali aggregate reaction.

Polymethyl methacrylate (PMMA), on the other hand, is a polymer polymerized with monomer methyl methacrylate (MMA). The PMMA resin is used for contact lenses, artificial joints and bones for medical purposes, and unlike cement paste, it is harmless to the human body. In addition, unlike cement pastes made of irregular bonded structures or pastes using other chemical additives, PMMA resin is a polymer material formed of a regular bonding structure, and has a triple structure in which long carbon molecule rings are formed by chemical curing reaction. The reaction mechanism of PMMA resin is made by adding an initiator such as benzoyl peroxide to MMA, and the reaction mechanism is as shown in FIG.

As such, PMMA resins form a regular binding structure and have high molecular weights to accurately obtain chemical properties, and added initiators accurately meet MMA molecules to promote reactions that accelerate the formation of polymers, and the probability that molecules and molecules meet It is at least 98%, so it does not interfere with chemical properties after completion of curing.

When such a polymer material is mixed with the low ash, it is possible to overcome problems such as low physical incomplete particle size distribution, porosity and low strength of low ash itself.

The resin of the present invention is a PMMA obtained by polymerizing such MMA with a separate initiator, and it is more preferable to dissolve PMMA in MMA and then polymerize it in order to shorten the polymerization time while satisfying desired physical properties such as strength and molecular weight. In this case, the weight ratio of PMMA to MMA is preferably 1: 1 to 10 weight ratio, but if the amount of MMA is less than the above range, the PMMA is not completely dissolved, whereas if it exceeds the above range, the polymerization time is unnecessarily longer or the molecular weight is low. There are disadvantages.

The resin of the present invention may express the effects of the present invention even if the MMA resin alone is used, but it is more preferable to mix with the urethane-acrylate resin.

Urethane-acrylate resin refers to a resin that is polymerized by introducing a hydrophilic functional group into a urethane prepolymer having a urethane bond (~ NH-COO ~) in a polymer chain and mixing it with an acrylate monomer to polymerize the urethane-acrylate resin. It has excellent mechanical strength such as strength, tear strength, elongation and wear resistance, and has been applied in various fields throughout the industry. The urethane-acrylate resin is a resin that combines the properties of urethane and acryl and belongs to a hybrid resin, which is a hybrid material obtained by polymerizing two or more polymer materials. The preparation of urethane-acrylate resins typically involves urethane prepolymers, which are polymers of polyols and isocyanates, and methyl methacrylates (MMA), ethyl acrylates, acrylic acids, and 2-hydrides, which are acrylic emulsions. It is made by mixing hydroxy alkyl acrylates such as oxy ethyl methacrylate and n-butyl acrylate.

The polyol and isocyanate constituting the urethane prepolymer is not limited as long as it is a substance capable of urethane bonding, but in the case of polyol, ethylene glycol, propylene glycol, tetramethylene glycol, poly (tetramethylene ether) glycol, and poly (1,4-butanediol adi) Pate) glycol, polycaprolactonediol glycol, polycarbonate diol and mixtures thereof are preferable, and in the case of isocyanate, polymethylene diisocyanate, tolylene diisocyanate, naphthalene-1,5-diisocyanate, xylene di Isocyanates, diphenyl diisocyanates, diphenylmethane diisocyanates, triphenylmethane diisocyanates, 2,4-tolylene diisocyanate dimers, hexamethylene diisocyanates, isophorone diisocyanates and mixtures thereof It is preferred.

The range of average molecular size of such urethane-acrylate may vary depending on the mixing ratio of polyurethane and acrylate emulsion, but is typically 95 nm (0% polyurethane, 100% acrylate) to 230 nm (70% polyurethane, Acrylate 30%) range.

In general, urethane-acrylate resins are somewhat inferior in strength but have high elasticity, so they have excellent elasticity against temperature changes, and are applied to rooftop waterproofing materials, flooring materials for sports facilities, and crack repair to fill cracked areas. The products are different and the difference in strength occurs depending on the materials to be mixed.

Therefore, when the urethane-acrylate resin having good elasticity and elasticity is mixed and applied to the low ash together with the strong PMMA resin, some of them may be absorbed and expressed with an elastic force against external loads, thereby having high effective high functionality.

The molecular weight of the polymer resin mixed in this way is between 20,000 to 60,000 depending on the mixing ratio, and due to the high molecular weight, it is rarely recycled and recycled when properly mixed with low ash alone or other fillers such as sand with low ash. It can greatly improve the efficiency and utilization of the low-cost resource recycling.

The production rate of the polymer resin may be changed according to the required strength, and as a specific example, the mixing ratio of the polymer resin generally applied to manufacture the sidewalk block is

10 to 99.9% by weight of a methacrylate mixture of MMA and PMMA, and

Urethane-acrylate resin 0.1-90 wt%

.

The initiator used herein is not limited as long as it is an initiator capable of initiating acrylate and urethane polymerization including MMA, but in particular potassium persulfate, ammonium persulfate, sodium hydrosulfite, sodium persulfate, sodium bisulfite, sodium bis Preference is given to an initiator selected from the group consisting of sulfate, rongalite C, rongallite Z, benzoyl peroxide, t-butyl hydroperoxide, N, N'-azobisisobutyronitrile and mixtures thereof. Furthermore, it is preferable that the content of the initiator is 1 to 15 parts by weight per 100 parts by weight of the resin mixture. If the content is less than the above range, the polymerization takes too long. There are disadvantages.

In addition to the above initiators, the block composition of the present invention may be used by adding other additives such as dispersing agents, antifoaming agents, and neutralizing agents generally used in the production of the resin composition.

In the case of low ash, it usually contains water, but if it is manufactured without a separate water removal equipment, it may be prepared by including a separate additive or a small amount of cement for water reduction.

In order to enhance the strength of the material, fillers other than polymer resin may be used, and fillers that may be used are generally cement, fly ash, sand, gravel, stone powder, silica sand, calcium carbonate, talc, steelmaking. Fillers selected from the group consisting of slag and mixtures thereof may be included but are not particularly limited.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described.

Example

Example 1 Preparation of Binder Resin

70 g of polymethyl methacrylate (LG MMA. Korea) was dissolved in 350 g of methyl methacrylate (Dasan MMA. Korea), and then polymerized at 70 DEG C, and then 12 g of n-butyl acrylate was added thereto. Add to mix. Separately, 10 g of poly (tetramethylene ether) glycol (BASF.Germany) and 9.5 g of hexamethylene diisocyanate (Asahi Kasei. A hydrophilic functional group was introduced, 10 g of 2-hydroxy ethyl methacrylate (Aldrich. USA) were mixed and polymerized at 90 ° C., and 2 g of triethylamine (Junsei Chemical. The urethane-acrylate resin was prepared by stirring while rapidly lowering the temperature to ° C. 50 g of the urethane-acrylate resin thus prepared was added to the methacrylate mixture to prepare a binder resin composition of the present invention.

Example 2: Sidewalk Block

To 5 g of the binder resin of Example 1 was added 74 g of low ash containing water as shown in FIG. 3, 20 g of a filler mixed with cement and fly ash in 50:50, 1 g of benzoyl peroxide was mixed and A specimen (300 mm × 300 mm × 55 mm) was produced.

In preparing the specimen, the resin composition was put in a square wooden formwork and the air in the formwork was removed using a rubber hammer. After storage for 7 days, the formwork was removed and the flexural strength test was performed using a Universal Testing Machine (UTM).

Test The test method was carried out in compliance with KS F 4419, the standard test for block flexural strength for sidewalks. The test test method and the bending strength measurement foreground are shown in FIG. 5.

Example 2: Shore Block

To 15 g of the resin prepared in Example 1 was added 35 g of a mixture of sand and gravel (13 mm) at 50:50, 10 g of reclaimable stone powder, 10 g of other filler calcium carbonate, and 30 g of low ash. In addition, 1 g of benzoyl peroxide was mixed to prepare a lake block as shown in FIG. 6, and compression molding was performed at a load of 50 ton _f by using a press machine used for manufacturing the lake block to enhance strength. An ophthalmic block of 400 mm x 80 mm was prepared.

Test Example

In the test of specimens of Examples 2 and 3, the specimens were immersed in water for 24 hours according to KS regulations as shown in FIG. 7, and immediately removed and placed as shown in FIG. At this time, the pressurization speed was applied at a high speed up to about 50% of the breaking load, and then the maximum load indicated in the tester was applied so that the increase in maximum bending compressive stress did not exceed 9.8 MPa (= N / mm ² ) per minute. The load P was measured. The measured results are shown in Table 1 and Table 2 below.

sample Load (N) Flexural strength (MPa) KS F 4419 Flexural Strength Standard (MPa) Example 2 (A Block) 16,937.50 8.63 5.0 or more satisfied Example 3 (B Block) 13,062.50 6.86 satisfied

As a result of the test, it can be seen that when the block for the road block was manufactured by minimizing the polymer resin and maximizing the amount of low ash used up to 74% by weight, the KS standard strength was higher than 5.0 MPa. This shows that the polymer material owned by the resin itself can be recycled by supplementing the low physical properties. As shown in Example 3, the application range is varied by improving the strength when adjusting the polymer resin ratio and additive amount. It can be seen that it can be made.

In the above description of the preferred embodiment of the present invention, the present invention is not limited to the specific embodiments described above, those skilled in the art various modifications without departing from the gist of the present invention Of course it is possible. Accordingly, the scope of the present invention should not be construed as being limited to the above-described embodiments, but should be determined by equivalents to the appended claims, as well as the following claims.

Claims (8)

Polymethyl methacrylate: methyl methacrylate = 1: 100 parts by weight of the resin mixture in a ratio of 1 to 10 parts by weight;
100 to 2000 parts by weight of bottom ash filler; And
1 to 15 parts by weight of initiator
Block composition comprising a. The method according to claim 1,
The resin mixture is
Polymethyl methacrylate: methyl methacrylate = 1: 10 to 99.9% by weight methacrylate mixture in a ratio of 1 to 10, and
Urethane-acrylate resin 0.1-90 wt%
Block composition characterized in that the mixture of polymerized. The method according to claim 1,
The low ash filler is
Low ash 10 to 99.9% by weight, and
0.1 to 90% by weight of filler material selected from the group consisting of cement, fly ash, sand, gravel, stone powder, silica sand, calcium carbonate, talc, steel slag and mixtures thereof
Block composition, characterized in that the mixture of. The method according to claim 1,
The initiators include potassium persulfate, ammonium persulfate, sodium hydrosulfite, sodium persulfate, sodium bisulfite, sodium bisulfate, rongalite C, rongalite Z, benzoyl peroxide, t-butyl hydroperoxide And an initiator selected from the group consisting of N, N'-azobisisobutyronitrile and mixtures thereof. The method according to claim 2,
The isocyanate which is a monomer of the urethane prepolymer of the urethane-acrylate resin is polymethylene diisocyanate, tolylene diisocyanate, naphthalene-1,5-diisocyanate, xylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, Block composition, characterized in that the isocyanate selected from the group consisting of triphenylmethane diisocyanate, 2,4-tolylene diisocyanate dimer, hexamethylene diisocyanate, isophorone diisocyanate and mixtures thereof. The method according to claim 2,
The polyol which is a monomer of the urethane prepolymer of the urethane-acrylate resin is ethylene glycol, propylene glycol, tetramethylene glycol, poly (tetramethylene ether) glycol, poly (1,4-butanediol adipate) glycol, polycaprolactonediol glycol, Block composition, characterized in that the polycarbonate selected from the group consisting of polycarbonate diol and mixtures thereof. The method according to claim 2,
The acrylic monomer of the urethane-acrylate resin is a block characterized in that the monomer selected from the group consisting of ethyl acrylate, acrylic acid, n-butyl acrylate, methyl methacrylate, 2-hydroxy ethyl methacrylate and mixtures thereof. Composition. The block which hardened the block composition of any one of Claims 1-7.

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